Article
Chemistry, Physical
Nasrin Ghanbari, Saeed Zakavi
Summary: This study reported the chemical scavenging reaction of singlet oxygen by iodobenzene in the presence of (triethyleneglycol)monomethyl ether, resulting in the formation of almost spherical nano-structured iodosylbenzene in water, water/acetonitrile, and acetonitrile. By using a polymer supported cationic porphyrin as the photosensitizer, the oxidation of organic substrates was achieved. A strategy of synthesizing a reactive secondary oxidant was proposed to overcome the short lifetime of singlet oxygen in organic solvents and water.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Haifa Alharbi, Mohamed Elsherbini, Jihan Qurban, Thomas Wirth
Summary: A library of novel C-N axially chiral iodoarenes was successfully synthesized from commercially available aniline derivatives in a three-step synthesis. These novel chiral iodoarenes were found to have potential as organocatalysts for stereoselective oxidative transformations, with good stereochemical control observed in the oxidation of propiophenone.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Tino P. Golub, Ayham H. Abazid, Boris J. Nachtsheim, Christian Merten
Summary: In this study, vibrational circular dichroism (VCD) spectroscopy was used as an experimental technique to verify DFT-calculated chiral iodane structures. The research revealed that an undescribed cationic chiral iodane was the most common intermediate under oxidative conditions, with significant intramolecular interactions and no significant interactions with potential anionic ligands. Aggregation of the substrates resulted in the formation of a non-coordinating anionic hydrogen bonded complex.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Lachlan Sharp-Bucknall, Tania, Jason L. Dutton
Summary: This article describes the synthesis and structural characterization of NO2-PhI(OTf)(2), a compound that is resistant to decomposition and has higher reactivity than previously misidentified PhI(OTf)(OAc), confirming the non-existence of PhI(OTf)(2) as an intermediate in oxidation reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Mohamed Elsherbini, Arnaud Osi, Haifa Alharbi, Fatemah Karam, Thomas Wirth
Summary: Chiral hypervalent iodine reagents play an important role in modern stereoselective organic synthesis. Although structurally diverse chiral hypervalent iodine reagents have been synthesized and extensively studied, hypervalent iodine reagents containing a chiral sulfur stereogenic center are rare and difficult to synthesize. In this study, a small library of iodoarenes containing chiral sulfinamide and chiral sulfoximine moieties was synthesized. The oxidation of chiral iodoarene precursors to iodine(III) reagents was challenging due to facile overoxidation of the sulfoxide moiety and loss of chirality. However, oxidation of chiral sulfonimidoyl derivatives was successful and led to novel sulfur-based chiral iodine(III) reagents.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Xiaotao Zhang, Miaomiao Liu, Hao Ge, Zhipeng Zhang
Summary: A class of confined chiral hypervalent iodines, designed by incorporating two sterically demanding BINOL-derived units, demonstrated good-to-excellent enantioselectivities in the α-oxysulfonylation of ketones (up to 97.5:2.5 er) and the oxidative cyclization of 5-oxo-5-arylpentanoic acids to γ-butyrolactones (up to 98:2 er), showing the effectiveness of this catalyst design strategy.
Article
Biochemistry & Molecular Biology
Liang Yang, Christian Marcus Pedersen
Summary: Protected 2-O-benzyolated glycosyl formates were synthesized in one-step from the corresponding orthoester using formic acid as the sole reagent. Glucopyranosyl, mannopyranosyl and galactopyranosyl donors were synthesized and their glycosylation properties were studied. Bismuth triflate was the preferred catalyst and KPF6 was used as an additive. The glycosylations showed excellent 1,2-trans-selectivities and high yields.
Article
Chemistry, Multidisciplinary
Masaki Fujie, Kyohei Mizufune, Yoshihiro Nishimoto, Makoto Yasuda
Summary: Proximal aryl C-H sulfonyloxylation and acetoxylation on 2-iodo-1,1-biphenyl structures have been achieved using λ3-iodane as a catalyst. The key step in this reaction involves intramolecular electron transfer between cationic I(III) and proximal 2-Ar groups in 2-arylphenyl-lambda 3-iodanes, leading to the generation of an iodanyl radical intermediate with a radical cationic Ar moiety. This intermediate then undergoes nucleophilic addition of acetate or sulfonate. The proposed mechanism is supported by electron spin resonance experiments. A 2-benzyl-iodobenzene structure is also compatible with this reaction system.
Review
Chemistry, Organic
Irina A. Mironova, Stefan F. Kirsch, Viktor V. Zhdankin, Akira Yoshimura, Mekhman S. Yusubov
Summary: This review summarizes recent approaches to the direct synthesis of organic azides using hypervalent iodine reagents. The first part discusses the use of unstable azidoiodinanes generated in situ, while the second part focuses on the application of stable azidobenziodoxoles as azidating reagents. The use of azidobenziodoxoles allows for selective direct azidation of specific bonds under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Correction
Chemistry, Multidisciplinary
Nina Declas, John R. J. Maynard, Laure Menin, Natalia Gasilova, Sebastian Gotze, Jakob L. Sprague, Pierre Stallforth, Stefan Matile, Jerome Waser
Summary: Correction for the paper 'Tyrosine bioconjugation with hypervalent iodine' by Nina Declas et al. presents an improved method for the effective conjugation of tyrosine with hypervalent iodine by rectifying the errors in the original study.
Article
Chemistry, Organic
Xia Wang, Peng Yang, Bo Hu, Qian Zhang, Dong Li
Summary: A novel transformation of primary amides to secondary amides was developed using hypervalent iodine reagents, promoting a Hofmann-type rearrangement to generate an isocyanate intermediate which was then trapped by a carboxylic acid from the same reagent to provide the corresponding secondary amides. This method not only offers an easy and efficient route for synthesizing secondary amides from primary amides, but also reveals novel reactivities of hypervalent iodine reagents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Chenyang Wang, Peng Shi, Carsten Bolm
Summary: In this study, dichloro- and dibromomethane were utilized as halogen sources to convert NH-sulfoximines to N-halo derivatives, using an in situ formed sulfoximidoyl-containing hypervalent iodine reagent under visible light. The reactions were carried out in air without the need for catalysts or additives, and the products were obtained in good to excellent yields.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Chemistry, Applied
Akira Yoshimura, Akio Saito, Viktor V. Zhdankin
Summary: Hypervalent iodine compounds, particularly those based on the benziodoxole heterocyclic system, are widely used as reagents and catalysts in modern organic chemistry. These cyclic hypervalent iodine reagents exhibit higher stability compared to their acyclic analogues, allowing for the safe handling and preparation of reagents with special ligands such as azido, cyano, and trifluoromethyl groups. They have been utilized for the transfer of substituents on hypervalent iodine to organic substrates under various reaction conditions. This review focuses on the recent synthetic applications of cyclic hypervalent iodine(III) reagents with different ligands, including N-3, NHR, CN, CF3, SCF3, OR, OAc, ONO2, and C(=N-2)CO2R, mainly in the past 5 years.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Lachlan Barwise, Jason D. Bennetts, Keith F. White, Jason L. Dutton
Summary: The synthesis and crystallographic characterization of NO2-C6H4-I(NTf2)(2) (NTf2 = bistriflimide) are reported. Experimental results demonstrate that this compound is capable of performing oxidation reactions that ArI(OTf)2 is unable to. Theoretical analysis indicates that Ar-I(NTf2)(2) is the most oxidizing compound among the known ArIL2 class of compounds, and it may also be the most oxidizing compound among the practically possible compounds in this class.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Jiang Nan, Xin Ren, Qiang Yan, Shilei Liu, Jing Wang, Yangmin Ma, Michal Szostak
Summary: A novel hypervalent iodine-induced twofold oxidative coupling of amines with amides and thioamides has been established, which chemoselectively assembles oxazoles and thiazoles. The mechanism involves the generation of ureas and thioureas as intermediates. These findings open up new avenues for exploring oxidative bond chemistry of amides and thioamides.
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
